Use of an oxidizing system comprising a macrocyclic metal complex and an oxidizing agent for removing excess, unfixed dye from dyed, textile materials

ABSTRACT

The use of an oxidizing system comprising a macrocyclic metal complex and an oxidizing agent removes excess, unfixed dye from dyed, textile materials after dyeing without the actual dyeing of the textile material being attacked. The oxidizing system is preferably used in at least one of the post-dyeing rinse steps.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to the use of an oxidizing system, comprising a macrocyclic metal complex and an oxidizing agent for removing excess, unfixed dye from dyed textile materials, and the resulting textiles.

[0003] 2. Brief Description of the Prior Art

[0004] U.S. Pat. No. 6,099,586 and WO-A-02/16330 disclose specific macrocyclic metal complexes useful as bleach activators. Combined with a peroxide source, preferably hydrogen peroxide, these bleach activators make it possible to carry out oxidation reactions. Such oxidation reactions are carried out for example in paper bleaching, for decolorizing coloured wastewaters or in the desulphurization of motor fuels. Also described is the use in household laundry detergents for respectively removing and decolorizing soil on the laundry and in the wash liquor. In all these applications, the use of the specific macrocyclic metal complexes leads to an improvement in the results compared with the sole treatment with a peroxide source.

[0005] There is a fundamental problem in the textile industry with removing excess, unfixed dye from textiles after dyeing or printing. The colouring of textile material, i.e., printing or dyeing, will hereinafter be circumscribed using the term “dyeing”.

[0006] To remove unfixed dye, the dyer has to carry out a very time- and cost-intensive washing operation after the actual dyeing. This is the only way of achieving consumer quality with regard to washing, rubbing and staining fastness. One approach to shortening the washing operation after the dyeing of textile material was demonstrated in WO-A 92/18687 and EP-A-01 045 934 with reference to the use of enzymatic-based additive systems.

SUMMARY OF THE INVENTION

[0007] It has now been found that, surprisingly, the use of an oxidizing system comprising a macrocyclic metal complex and an oxidizing agent provides excellent decolorization of excess, unfixed dye from dyed textile materials.

[0008] This process advantageously provides highly selective removal of excess, unfixed dye from the dyed textile, without the dyed textile itself being decolorized.

[0009] The invention accordingly provides for the use of an oxidizing system comprising the two components

[0010] 1) a macrocyclic metal complex of the general formula (1)

[0011] where

[0012] Y₁, Y₃ and Y₄ are each independently a single bond or a bridge member which contains 1, 2 or 3 carbon atoms in the bridge,

[0013] Y₂ is a bridge member having at least 1 carbon atom in the bridge,

[0014] R is independently in each occurrence hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy, phenoxy, CH₂CF₃ or CF₃ or two R radicals which are bound to the same carbon atom combine to form a substituted or unsubstituted benzene, cycloalkyl or cycloalkenyl ring, the carbon atom to which the two R radicals are bound being part of the benzene, cycloalkyl or cycloalkenyl ring,

[0015] M is a transition metal in the oxidation states I, II, III, IV, V or VI or is selected from groups 6, 7, 8, 9, 10 and 11 of the periodic table,

[0016] Q is a counterion which balances the charge of the macrocyclic metal complex on a stoichiometric basis, and

[0017] L is a further ligand

[0018] and

[0019] 2) an oxidizing agent for removing excess, unfixed dye from dyed textile materials.

DETAILED DESCRIPTION OF THE INVENTION

[0020] The invention is described more fully hereunder with particular reference but without limitation to its preferred embodiments. Preferably, in the macrocyclic metal complex of the general formula (1)

[0021] Y₁, Y₃ and Y₄ are each independently a (—CH₂—)_(x) group, where x is 1, 2 or 3 and one or more hydrogen atoms in the (—CH₂—)_(x) group may be substituted by an R^(i) radical, R^(i) being alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy, or two R^(i) radicals which are bound to two adjacent carbon atoms of the (—CH₂—)_(x) group combining to form a benzene, cycloalkyl or cycloalkenyl ring which may contain one or more hetero atoms, preferably N, O or S.

[0022] Preferably, in the macrocyclic metal complex of the general formula (1)

[0023] Y₂ is a bridge member having 1, 2 or 3 carbon atoms in the bridge, preferably a (—CH₂—)_(y) group, where y is 1 or 2 and one or more hydrogen atoms in the (—CH₂—)_(y) group may be substituted by an R^(ii) radical, R^(ii) being alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy, or two R^(ii) radicals which are bound to two adjacent carbon atoms of the (—CH₂—)_(y) group combining to form an optionally substituted benzene, cycloalkyl or cycloalkenyl ring which may contain one or more hetero atoms, preferably N, O or S, preferably a benzene ring which may be substituted by electron-donating or electron-withdrawing radicals.

[0024] In the macrocyclic metal complex of the general formula (1)

[0025] the R radicals are each independently hydrogen, C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₄-C₁₂-cycloalkenyl, C₂-C₈-alkenyl, C₆-C₁₄-aryl, C₂-C₁₂-alkynyl, C₁-C₁₂-alkylaryl, halogen, alkoxy, phenoxy, CH₂CF₃ or CF₃ or two R radicals which are bound to the same carbon atom combined to form a substituted or unsubstituted benzene, C₃-C₈-cycloalkyl or C₄-C₁₂-cycloalkenyl ring, the carbon atom to which the two R radicals are bound being part of the benzene, cycloalkyl or cycloalkenyl ring.

[0026] The metal M in the macrocyclic metal complex of the general formula (1) is a transition metal having the oxidation states I, II, III, IV, V or VI or from groups 6, 7, 8, 9, 10 or 11 of the periodic table. Preferably, the metal M represents Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and/or Pt. Mixtures of metals of the aforementioned oxidation states or from the aforementioned groups of the periodic table are likewise possible.

[0027] Q in the macrocyclic metal complex of the general formula (1) is a counterion which balances the charge of the macrocyclic metal complex on a stoichiometric basis. The metal-ligand complex is customarily negative, preferably −1. Consequently, the counterion generally has a positive charge, given a preferred negative charge of −1, is accordingly +1.

[0028] Suitably, Q is an alkali metal counterion, preferably potassium, lithium or sodium, NR^(iii) ₄ ⁺ or PR^(iii) ₄ ⁺, where every R^(iii) is independently hydrogen, alkyl, aryl, alkylaryl, alkenyl or joins to form a cycloalkyl, cycloalkenyl or aryl ring which optionally contains one or more hetero atoms, preferably oxygen, sulphur or nitrogen.

[0029] L is any further ligand which can attach to M. Preferably, L is a labile ligand, especially H₂O, Cl or CN.

[0030] The aforementioned preferred and particularly preferred meanings for Y₁-Y₄, R, R^(i), R^(ii), R^(iii), Q and L may be combined in any desired manner.

[0031] In a preferred embodiment, the invention comprises the use of an oxidizing system which comprises a macrocyclic metal complex which has the general formula (1A)

[0032] where

[0033] X and Z are each independently hydrogen, electron-donating or electron-withdrawing groups,

[0034] R^(iv) and R^(v) may each independently be hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy radicals or combine to form a cycloalkyl or cycloalkenyl ring which may contain one or more hetero atoms, preferably oxygen, sulphur or nitrogen,

[0035] M is a transition metal of the oxidation states I, II, III, IV, V or VI or is selected from groups 6, 7, 8, 9, 10 or 11 of the periodic table,

[0036] Q is a counter ion which balances the charge of the macrocyclic metal complex on a stoichiometric basis, and

[0037] L is a further ligand.

[0038] In the macrocyclic metal complex of the formula (1A), X and Z may each be independently hydrogen or electron-donating or electron-withdrawing radicals. Electron-donating or electcron-withdrawing radicals change the electron density of the metal-ligand complex and thus influence its reactivity.

[0039] Suitable electron-withdrawing radicals are for example halogens, preferably chlorine, bromine or iodine, more preferably chlorine, SO₃ ⁻, OSO₃ ⁻, OSO₃R^(vi) (where R^(vi) is hydrogen, alkyl, aryl or alkylaryl) or NO₂ ⁻.

[0040] Suitable electron-donating radicals are for example C₁-C₈-alkoxy, preferably methoxy, ethoxy, propoxy and butoxy, C₁-C₈-alkyl, preferably methyl, ethyl, propyl, n-butyl and tert-butyl, and hydrogen.

[0041] In the macrocyclic metal complex of the formula (1A), R^(iv) and R^(v) are each independently hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, halogen, alkoxy or phenoxy radicals. R^(iv) and R^(v) are preferably each independently alkyl, particularly preferably C₁-C₅-alkyl. More preferably R^(iv) and R^(v) are both identically methyl or ethyl. Even more preferably, R^(iv) and R^(v) combine to form a cycloalkyl ring, especially a cyclopentyl or cyclohexyl ring, or a cycloalkenyl ring. This cycloalkyl or cycloalkenyl ring may contain one or more hetero atoms, preferably oxygen, sulphur or nitrogen.

[0042] The metal M in the macrocyclic metal complex of the general formula (1a) is a transition metal having the oxidation states I, II, III, IV, V or VI or is selected from groups 6, 7, 8, 9, 10 or 11 of the periodic table. Preferably, the metal M represents Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and/or Pt. Mixtures of metals of the aforementioned oxidation states or from the aforementioned groups of the periodic table are likewise possible.

[0043] Q in the macrocyclic metal complex of the general formula (1a) is a counterion which balances the charge of the macrocyclic metal complex on a stoichiometric basis. The metal-ligand complex is customarily negative, preferably −1. Consequently, the counterion generally has a positive charge, given a preferred negative charge of −1, is accordingly +1.

[0044] Suitably, Q is an alkali metal counterion, preferably potassium, lithium or sodium, NR^(iii) ₄ ⁺ or PR^(iii) ₄ ⁺, where every R^(iii) is independently hydrogen, alkyl, aryl, alkylaryl, alkenyl or combines to form a cycloalkyl, cycloalkenyl or aryl ring which optionally contains at least one further atom, as carbon.

[0045] In the macrocyclic metal complex of the general formula (1A) L is any further ligand which can attach to M. Preferably, L is a labile ligand, especially H₂O, Cl or CN.

[0046] The preparation of the macrocyclic metal complexes used in accordance with the invention is described in EP-A-918 840, U.S. Pat. No. 6,099,586 and WO-A-02/16330, each of which is hereby explicitly incorporated herein by reference.

[0047] The oxidizing agent can be any organic or inorganic oxidizing agent. A peroxy compound is typically used. Suitable peroxy compounds are hydrogen peroxide, hydrogen peroxide adducts, compounds capable of releasing or generating hydrogen peroxide in aqueous solution, organic peroxides, persulphates, perphosphates and persilicates.

[0048] Hydrogen peroxide adducts include alkali metal, preferably sodium, lithium or potassium, carbonate peroxyhydrate and also urea peroxide.

[0049] Compounds capable of generating hydrogen peroxide in aqueous solution include alkali metal, preferably sodium, potassium or lithium, perborate (as mono- or tetrahydrate). Such perborates are commercially available.

[0050] Alternatively, an alcohol oxidase and its appropriate alcohol substrate can be used as peroxide source.

[0051] Organic peroxides include benzoyl and cumene hydroperoxides.

[0052] Persulphates include peroxymonosulphate and Caro's acid.

[0053] Particularly preferred oxidizing agents are hydrogen peroxide and sodium perborate.

[0054] The macrocyclic metal complex is used in the oxidizing system in an amount in the range from 0.01 μmol to 1000 μmol. Preference is given to an amount in the range from 0.1 μmol to 100 μmol.

[0055] The oxidizing agent is used oxidizing system in an amount in the range of 0.01-1000 mmol. Preference is given to an amount in the range of 0.1-100 ppm.

[0056] The inventive use is preferably carried out by the dyed textile material being contacted with the oxidizing system in at least one of the post-dyeing rinse steps.

[0057] The dyeing can be dyeing with any commercially available dye. Reactive dyes, direct dyes, substantive dyes, acid dyes, metal complex dyes, disperse dyes, vat dyes and sulphur dyes may be mentioned.

[0058] The dyeing has preferably been carried out with water-soluble dyes and more preferably with reactive dyes.

[0059] Preferably, the dyed textile material is contacted with the oxidizing system in at least one of the post-dyeing rinse steps by at least one of the rinse liquors having the two components of the oxidizing system added to it either individually in any order or else individually and concurrently.

[0060] More preferably, the dyed textile material is contacted with the oxidizing system in one of the post-dyeing rinse steps.

[0061] The macrocyclic metal complex is typically added in the form of an aqueous solution to which may optionally have been added 0.5-40% by weight, based on the entire solution, of a pH stabilizer and of a water-soluble or at least partially water-soluble solvent. As suitable water-soluble solvents there may be mentioned ethanol, methanol, isopropanol, ethylene glycol, diethylene glycol, polyethylene glycols, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, acetone, acetonitrile, acetamide, tetrahydrofuran, dioxane, dimethyl sulphoxide, dimethyl formamide, sulpholane or mixtures thereof. Suitable pH stabilizers are phosphate, citrate buffer, carbonate buffer or borate buffer, or mixtures thereof.

[0062] When hydrogen peroxide is used as oxidizing agent, it is used in the form of for example commercially available aqueous solutions having an assay of 3-50%.

[0063] It may be advantageous to use not only the oxidizing system in the inventive use but also further additives, such as detersive substances, preferably surfactants, sequestrants, defoamers, enzymes, such as amylases, pectinases, proteases, peroxidase, laccases or lipases, water-conditioning agents, such as water softeners, pH stabilizers, such as phosphate, citrate buffer, carbonate buffer or borate buffer, or mixtures thereof, or solvents which are soluble or at least partially soluble in water. Suitable water-soluble solvents are ethanol, methanol, isopropanol, ethylene glycol, diethylene glycol, polyethylene glycols, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, acetone, acetonitrile, acetamide, tetrahydrofuran, dioxane, dimethyl sulphoxide, dimethyl formamide, sulpholane or mixtures thereof.

[0064] Such additives are used at 0-50% by weight and preferably 0.01-30% by weight, based on the rinse liquor.

[0065] The treatment time of the dyed textile material in a rinse step depends on the type and amount of excess dye to be decolorized. Generally, 2-60 minutes are sufficient. If appropriate, a further addition of either any one or both of the components of the oxidizing system can be advantageous during the treatment.

[0066] The dyed textile materials may be cotton, filament viscose, staple viscose, lyocell, wool, silk, polyester, polyamide, polyacrylonitrile and elastane or blends thereof. The dyed textile materials are more preferably cotton, filament viscose and lyocell or blends thereof with polyester, polyamide or elastane.

[0067] The process for removing excess, unfixed dye is customarily carried out at a temperature of 25-95° C. and preferably 40-80° C. Rinse liquor pH is in the range of 4-13, preferably 5-12 and more preferably 7-11.

[0068] The invention is further described by the following illustrative but non-limiting examples.

EXAMPLE

[0069] The example hereinbelow utilizes a macrocyclic metal complex

[0070] which is prepared by the method described in Examples 1-6 of WO-A-02/16330. This compound is hereinbelow referred to as 1b.

[0071] The starting point is a scoured and bleached cotton formed-loop knit which is dyed in a laboratory dyeing machine (a Mathis Spectradye for example) at a liquor ratio of 10:1 using the following recipe:

[0072] 10 g of cotton are pretreated in a liquor consisting of  0.4 g/l of RESPUMIT ® NF  0.5 g/l of PERSOFTAL ® L and 80 g/l of sodium chloride

[0073] at 25° C. for 10 minutes. The temperature is raised to 50° C., when

[0074] 8% on weight of fibre of Remazol® Deep Black N,

[0075] is added in 3 portions at intervals of 10 minutes. This is followed, after a further interval of 10 minutes by the addition of 2.0 g/l of sodium carbonate in three portions at intervals of 10 minutes. This is followed after a further 10 minutes by the addition of 3.0 g/l of 50% aqueous sodium peroxide solution in three portions at intervals of 10 minutes. This is finally followed by heating to 60° C. at 1° C./min and then a 60 minute treatment at 60° C. Immediately following dyeing, the dyed sample is rinsed in a liquor ratio of 10:1 as follows:

[0076] drain the dyeing liquor

[0077] (1st rinse step) addition of fresh water, rinse at 60° C. for 10 minutes, drain the liquor

[0078] (2nd rinse step) addition of fresh water at 95° C. for 10 minutes, drain the liquor

[0079] (3rd rinse step) addition of fresh water together with 1 μmol of compound 1b, treat at 60° C. for 5 minutes, addition of 4.4 mmol of hydrogen peroxide, treat at 60° C. for 10 minutes, drain the liquor

[0080] (4th rinse step) addition of fresh water, rinse at 40° C. for 10 minutes and drain the liquor

[0081] Finally, the sample is centrifuged and dried.

[0082] A comparative test is carried out with the third rinse step being carried out without addition of compound 1b and without hydrogen peroxide. Otherwise all the steps are carried out in the same way.

[0083] The table below shows the colour of the individual rinse liquors (determined as absorbance at 598 nm; the lower the absorbance, the lower the colouredness): Inventive process Comparative test After: absorbance at 598 nm absorbance at 598 nm 2nd rinse step about 7.6 about 7.6 3rd rinse step 0.5 about 3.2 4th rinse step 0.3 1.2

[0084] The results clearly show the significantly better decolorization of the rinse liquor in bath 3 in the presence of compound 1b and hydrogen peroxide and the attendant lower colour of the last rinse liquor for the inventive process.

[0085] The wash-off effect is evaluated by determining the waterfastness of the dyeing in accordance with German standard specification DIN 54006 (waterfastness of dyeings, severe exposure). Cotton is used as adjacent fabric. The evaluation scale goes from 1 to 5, where 5 denotes the best fastness. Inventive process Comparative test Rating 2 2-3

[0086] The inventive process accordingly provides a substantial improvement in waterfastness by half a rating point.

[0087] The treatment with the inventive oxidizing system has not affected the dyeing on the cotton.

[0088] Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims. 

What is claimed is:
 1. A process for removing excess, unfixed dye from dyed textile materials comprising treating the dyed textile materials with an oxidizing system comprising the two components 1) a macrocyclic metal complex of the general formula (1)

where Y₁, Y₃ and Y₄ are each independently a single bond or a bridge member which contains 1, 2 or 3 carbon atoms in the bridge, Y₂ is a bridge member having at least 1 carbon atom in the bridge, R is independently in each occurrence hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy, phenoxy, CH₂CF₃ or CF₃ or two R radicals which are bound to the same carbon atom combine to form a substituted or unsubstituted benzene, cycloalkyl or cycloalkenyl ring, the carbon atom to which the two R radicals are bound being part of the benzene, cycloalkyl or cycloalkenyl ring, M is a member selected from the group consisting of transition metals in the oxidation states I, II, III, IV, V, VI and combinations thererof or is a member selected from groups consisting of 6, 7, 8, 9, 10, 11 of the periodic table and combinations thereof, Q is a counterion which balances the charge of the macrocyclic metal complex on a stoichiometric basis, and L is a further ligand and 2) an oxidizing agent
 2. The process according to claim 1, characterized in that the dyed textile material is contacted with the oxidizing system in at least one post-dyeing rinse step.
 3. The process according to claim 1, characterized in that in the macrocyclic metal complex of the general formula (1), Y₁, Y₃ and Y₄ are each independently a (—CH₂—)_(x) group, where x is 1, 2 or 3 and one or more hydrogen atoms in the (—CH₂—)_(x) group may be substituted by an R^(i) radical, R^(i) being alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy, or two R^(i) radicals which are bound to two adjacent carbon atoms of the (—CH₂—)_(x) group combining to form a benzene, cycloalkyl or cycloalkenyl ring which may contain one or more hetero atoms.
 4. The process according to claim 1, characterized in that in the macrocyclic metal complex of the general formula (1) Y ₂ is a bridge member having 1, 2 or 3 carbon atoms in the bridge, comprising a (—CH₂—)_(y) group, where y is 1 or 2 and one or more hydrogen atoms in the (—CH₂—)_(y) group is optionally substituted by an R^(ii) radical, R^(ii) being alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy, or two R^(ii) radicals which are bound to two adjacent carbon atoms of the (—CH₂—)_(y) group combining to form an optionally substituted benzene, cycloalkyl or cycloalkenyl ring which optionally contain one or more hetero atoms.
 5. The process of claim 4, characterized in that optionally the hetero atoms are one of N, O or S, and characterized in that optionally the substituted benzene ring is substituted by electron-donating or electron withdrawing radicals.
 6. The process according to claim 1, characterized in that in the macrocyclic metal complex of the general formula (1), the R radicals are each independently hydrogen, C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₄-C₁₂-Cycloalkenyl, C₂-C₈-alkenyl, C₆-C₁₄-aryl, C₂-C₁₂-alkynyl, C₁-C₁₂-alkylaryl, halogen, alkoxy, phenoxy, CH₂CF₃ or CF₃ or two R radicals which are bound to the same carbon atom combine to form a substituted or unsubstituted benzene, C₃-C₈-cycloalkyl or C₄-C₁₂-cycloalkenyl ring, with the carbon atom to which the two R radicals are bound being part of the benzene, cycloalkyl or cycloalkenyl ring.
 7. The process according to claim 1, characterized in that in the macrocyclic metal complex of the general formula (1) M is selected from the group consisting of Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd or Pt.
 8. The process according to claim 1, characterized in that in the macrocyclic metal complex of the general formula (1) Q is an alkali metal counterion, NR^(iii) ₄ ⁺ or PR^(iii) ₄ ⁺, where every R^(iii) is independently hydrogen, alkyl, aryl, alkylaryl, alkenyl or joins to form a cycloalkyl, cycloalkenyl or aryl ring which optionally contains one or more hetero atoms.
 9. The process according to claim 8, wherein the hetero atoms are oxygen, sulphur or nitrogen.
 10. The process according to claim 1, characterized in that in the macrocyclic metal complex of the general formula (1) L is a labile ligand.
 11. The process according to claim 10, wherein the labile ligand is H₂O, Cl or CN.
 12. The process according to claim 1, characterized in that a macrocyclic metal complex used has the general formula (1A)

where X and Z are each independently hydrogen, electron-donating or electron-withdrawing groups, R^(iv) and R^(v) are each independently hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy radicals or combine to form a cycloalkyl or cycloalkenyl ring which optionally contain one or more hetero atoms, M is a transition metal of the oxidation states I, II, III, IV, V, VI or is selected from the groups 6, 7, 8, 9, 10 or 11 of the periodic table, Q is a counter ion which balances the charge of the macrocyclic metal complex on a stoichiometric basis, and L is a further ligand.
 13. The process according to claim 12, characterized in that X and Z in the general formula (1A) are each independently halogen, SO₃ ⁻, OSO₃ ⁻, OSO₃R^(vi) where R^(vi) is hydrogen, alkyl, aryl or alkylaryl, NO₂ ⁻, C₁-C₈-alkoxy, C₁-C₈-alkyl, or hydrogen.
 14. The process according to claim 12, characterized in that in the macrocyclic metal complex of the formula (IA), R^(iv) and R^(v) are each independently hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, halogen, alkoxy or phenoxy radicals or combine to form a cycloalkyl ring, or a cycloalkenyl ring, where the cycloalkyl or cycloalkenyl ring optionally contains one or more hetero atoms.
 15. The process according to claim 14, characterized in that the alkyl is selected from the group consisting of C₁-C₅-alkyl, methyl and elthyl.
 16. The process according to claim 1, characterized in that the oxidizing agent comprises hydrogen peroxide, hydrogen peroxide adducts, urea peroxide, compounds capable of releasing or generating hydrogen peroxide in aqueous solution, perborate, organic peroxides, persulphates, or persilicates.
 17. The process according to claim 16, characterized in that the hydrogen peroxide adducts are selected from the group consisting of alkali metal, sodium, lithium and potassium.
 18. The process according to claim 16, characterized in that optionally the organic peroxides are benzoyl or cumene hydroperoxides; and optionally the persulphates are peroxymonosulphate or Caro's acid.
 19. The process according to claim 1, characterized in that the dyed textile material is contacted with the oxidizing system in at least one post-dyeing rinse step by at least one rinse liquor having the two components of the oxidizing system added to it either individually in any order or else individually and concurrently.
 20. The process according claim 1, characterized in that the dyed textile material is contacted with the oxidizing system in one post-dyeing rinse steps.
 21. The process of claim 1, characterized in that the dyed textile material was dyed with water-soluble dyes which are optionally reactive dyes.
 22. Dyed, textile material prepared by the process of claim
 1. 